JPWO2005108680A1 - Water control structure, concrete block for water control, and water control method using them - Google Patents

Abstract

A water purification body suitable for water control, with excellent material strength and economics, and excellent properties that contribute to water purification such as adsorptivity and microbial immobilization, was used as a crushing stone for dredging and sinking. In order to provide a water control structure, a concrete block for water control using the water purification body, and a water control method using the same, a binder and zeolite are mixed and fired as essential raw materials, and the composition Provided is a water purification body having a high strength, an ammonia adsorption property and an excellent microorganism adhesion property, wherein the zeolite component is less than 50% by weight.

Description

  The present invention relates to a water control structure in which a zeolite-containing water purification body having a specific composition is filled in a cage or a frame used for water control works such as revetments and sinking works in rivers and lakes, and the water purification body on the surface. The present invention relates to a fixed concrete block for water control, and a water control method using the same.

  There are various methods for water control such as bank protection and floor protection in rivers and lakes. For example, as a long-established construction method, for example, cobblestones or crushed stones are placed on a rectangular parallelepiped or a cylindrical wall. For example, there are rough slabs, wood sunks, and improved sunks that assemble a frame made of futon, gabion, wood, concrete, and cast iron, and crush the inside of the frame. In addition, after the period of high growth, the efficiency and strength of construction became important, and water construction using mainly concrete was widely used in place of the above dredging and sinking works.

  However, concrete construction mainly using concrete has the risk of destroying the ecosystems of various living creatures that inhabit it, and goes against the flow of thought to protect and create the natural environment that has been growing in recent years. To do. Therefore, in recent years, the above dredging and sinking work that can provide an environment suitable for inhabiting various organisms is being reviewed, and various technologies that improve their workability, strength, water purification, etc. Have been developed (for example, Japanese Unexamined Patent Publication No. 10-77620, Japanese Unexamined Patent Publication No. 2001-55716, Japanese Unexamined Patent Publication No. 2001-140240). Furthermore, a water control method using a concrete block taking into consideration the natural environment while taking advantage of the concrete has been developed (for example, Japanese Patent Laid-Open No. 2000-328574).

  On the other hand, zeolite is attracting attention as an environmentally conscious material that can adsorb water, soil, and substances that cause air pollution. This zeolite is a general term for microporous aluminosilicate crystals, and it exhibits excellent molecular adsorption, sieving action and ion exchange action due to the micropores of 1 nm or less and the negative charge of its skeleton. Widely used.

  A water purification body that makes use of the characteristics of zeolite is usually a fired body obtained by kneading, shaping, and firing zeolite together with a binder and water. As a prior art relating to such a calcined product, for example, a method for reducing the binder content to ensure zeolite adsorption and catalytic performance and to increase the zeolite content as much as possible (for example, Japanese Patent Application Laid-Open No. No. 2-160616) or a special binder such as sepiolite-type clay or attapulgite-type clay to ensure porosity and material strength according to the application (for example, Japanese Patent Application Laid-Open No. 11-246282) ) And the like.

  In addition, as a technology for utilizing zeolite for water purification of rivers, lakes, and the like, zeolite synthesized from coal ash as revetment concrete material as disclosed in Japanese registered utility model No. 3093415 and Japanese Unexamined Patent Publication No. 2000-26488. The thing which mixed the powder is also proposed.

  In the above dredging and sinking works, the water purification function is exerted by the action of microorganisms that naturally adhere to the surface of the cobbles filled in the gutters and frames. Natural stones such as cobblestones and crushed stones are not particularly excellent as microbial carriers, and they do not have an effective water purification function. Therefore, the water purification function is greatly affected, and it cannot be said that the function is excellent. In the prior art, the water purification function is improved by variously changing the arrangement, size, filling ratio, etc. of natural stones in the cage and frame, or by planting plants on natural stones. However, as long as natural stone is used as a cobblestone, it is clear that a dramatic improvement in the water purification function cannot be desired. Therefore, it can be said that in order to dramatically improve the water purification function in dredging and sinking, it is necessary to develop a water purification body having properties suitable for water control and use it as a cobblestone. Water purification bodies with properties suitable for use in water construction have not only excellent water purification functions, but also a raw material composition that is unlikely to destroy natural ecosystems, and have been exposed to water for a long time. However, various properties are required such as having an excellent strength that does not easily lose its shape, being maintenance-free and capable of maintaining its function over a long period of time, and capable of mass production and low cost.

  Here, it is conceivable to use the above-described prior art zeolite-containing fired body as a water purification body, but the conventional fired body uses 50 wt% or more of zeolite as a main component, or uses special clay. To become expensive. Furthermore, if 50 wt% or more of the main component of zeolite is blended, plasticity is remarkably lost, so that it is necessary to blend an organic binder, but the material strength of the fired body is lowered and the manufacturing cost is increased. Moreover, in order to ensure the intensity | strength of a calcination body, although baking is performed at high temperature of 800-1200 degreeC, a zeolite becomes amorphous by this and the problem that the useful chemical characteristic which a zeolite originally has is impaired. is there. Furthermore, there is a problem that it is difficult to achieve both material strength and molding freedom.

Further, zeolite has an excellent ammonia adsorption ability due to the ion exchange action, but has been said to be difficult to regenerate by microorganisms because of its strong adsorption power. In order to apply this to water purification, the problem of regeneration must be solved. In particular, when it is used for direct purification of rivers, lakes, ponds, etc., if it is taken out from the water every time it breaks through adsorption and processed, it will not be practically used even if only the cost is considered. That is, it is important that the zeolite adsorbent installed in water forms a biota capable of efficiently desorbing, nitrifying, and even denitrifying the adsorbed NH ₄ ⁺ by the action of microorganisms.

  For the reasons described above, it cannot be said that the conventional fired body is a water purification body having properties suitable for water production from the viewpoint of cost and strength.

  In addition, with concrete containing zeolite, there is a problem that the zeolite crystal structure does not remain stable for a long time in an alkaline environment in the concrete, and the useful chemical properties inherent in zeolite are impaired. . In addition, since the workability of concrete decreases due to water absorption of zeolite, the amount of zeolite that can be blended in the concrete is limited to 10 to 20 wt% of the amount of cement, and as a result, the pure zeolite component contained in the molded body is only a small amount Thus, it is considered difficult to exhibit the characteristics of zeolite as a molded product.

  In view of the above, the present invention uses only raw materials that are not likely to destroy the ecosystem, is capable of mass production, has low cost, has strength equal to or higher than that of concrete, has a high degree of freedom in molding, and is semi-permanent. A water purification structure suitable for water control construction that can maintain an excellent water purification function that is maintenance-free and can be used as a crushing stone for dredging and sinking. It aims at providing the concrete block for waterworks using a purification body, and the waterworks construction method using these.

  As a result of diligent studies to solve the above problems, the inventors have simultaneously satisfied the conflicting properties of porosity and strength properties by careful selection of the binder material and its blending ratio, and also satisfied the requirements of moldability and low cost. As a result, the present inventors have succeeded in producing a water purification body and have made the present invention.

  That is, the present invention is characterized by the following items (1) to (23).

  (1) Mixing and baking binder and zeolite as essential raw materials, and filling a water purification body having a zeolite component of less than 50% by weight in a container or frame used for water control. Characteristic water control structure.

  (2) The water control structure according to (1), wherein the binder includes a plastic clay raw material and / or a straw raw material.

  (3) The plastic clay raw material is one or more selected from the group consisting of Kibushi clay, Sasame clay, kaolin, shale clay and porcelain stone, as described in (2) above Water control structure.

  (4) The water control structure according to (2) or (3), wherein the plastic clay raw material has a particle size of 5 μm or less.

  (5) The water control structure according to (2), wherein the raw material for straw is one or more selected from the group consisting of feldspar, magnesite, dolomite, and limestone.

  (6) The zeolite is selected from the group consisting of natural zeolite, synthetic A-type zeolite, synthetic X-type zeolite, synthetic Y-type zeolite, coal ash synthetic A-type zeolite, coal ash synthetic X-type zeolite, and coal ash synthetic Y-type zeolite. 1 type or 2 types or more, The water control structure in any one of said (1)-(5) characterized by the above-mentioned.

  (7) The water control structure according to any one of (1) to (6) above, wherein a temperature during firing of the water purification body is 500 to 700 ° C.

(8) The water control structure according to any one of (1) to (7) above, wherein the water purification body has a specific surface area of 20 m ² / g or more and a bending strength of 2 MPa or more.

  (9) The water control structure according to any one of (1) to (8) above, wherein the water purification body has a hollow shape.

  (10) The water control structure according to any one of (1) to (9), wherein a plant is vegetated on the water purification body.

  (11) The water control structure according to the above (10), wherein the plant is at least one selected from the group consisting of reed, catfish and makomo.

  (12) A water purification body in which a binder and zeolite are mixed and fired as essential raw materials and the zeolite component in the composition is less than 50% by weight is fixed on the concrete block surface, and / or concrete. A concrete block for water control, characterized in that it is contained inside porous concrete placed on the surface of the block.

  (13) The concrete block for water control according to (12), wherein the binder contains a plastic clay raw material and / or a straw raw material.

  (14) The plastic clay raw material is one or more selected from the group consisting of Kibushi clay, Sasame clay, kaolin, shale clay and porcelain stone, as described in (13) above Concrete block for waterworks.

  (15) The concrete block for water control according to the above (13) or (14), wherein the plastic clay raw material has a particle size of 5 μm or less.

  (16) The concrete block for water control according to (13), wherein the raw material for dredging is one or more selected from the group consisting of feldspar, magnesite, dolomite, and limestone.

  (17) The zeolite is selected from the group consisting of natural zeolite, synthetic A-type zeolite, synthetic X-type zeolite, synthetic Y-type zeolite, coal ash synthetic A-type zeolite, coal ash synthetic X-type zeolite, and coal ash synthetic Y-type zeolite. The concrete block for water control works according to any one of the above (12) to (16), wherein the concrete block is one type or two or more types.

  (18) The concrete block for water control according to any one of the above (12) to (17), wherein a temperature during firing of the water purification body is 500 to 700 ° C.

(19) The concrete for water control construction according to any one of the above (12) to (18), wherein the water purification body has a specific surface area of 20 m ² / g or more and a bending strength of 2 MPa or more. block.

  (20) The concrete block for water control according to any one of the above (12) to (19), wherein the water purification body has a hollow shape.

  (21) The concrete block for water control according to any one of the above (12) to (20), wherein a plant is vegetated on the water purification body.

  (22) The concrete block for water control according to the above (21), wherein the plant is at least one selected from the group consisting of reed, gama and makomo.

  (23) The water control structure according to any one of the above (1) to (11) and / or the concrete block for water control according to any one of the above (12) to (22) Or a water control method characterized by being installed at the bottom.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the water purification body suitable as a clog in water control construction, the water control structure using this, and the concrete block for water control construction, As a result, it is low-cost, high It is possible to provide a water control system that can efficiently purify water with low energy consumption and can greatly contribute to the conservation and creation of the natural environment.

  In addition, according to the present invention, zeolite synthesized from waste materials such as coal ash can be used, which can greatly contribute to the construction of a recycling society.

  This application is accompanied by a priority claim based on a Japanese patent application previously filed by the same applicant, ie, 2004-142178 (filing date: May 12, 2004), see this specification. Is incorporated here for:

FIG. 1 is a perspective view showing an embodiment of a water purification body according to the present invention. FIG. 2 is a perspective view showing an embodiment of the concrete block for water control according to the present invention. FIG. 3 is a perspective view showing an embodiment of the water control structure of the present invention. FIG. 4 is a perspective view showing an embodiment in which a plant is vegetated in the water control structure of the present invention. FIG. 5 is a perspective view showing an embodiment in which a plant is vegetated in the water control structure of the present invention. FIG. 6 is a cross-sectional view showing an embodiment of a state where the water control structure of the present invention is stacked on the river bank in a multistage manner to protect the bank. FIG. 7 is a graph showing the correlation between the amount of zeolite blended in the water purification body (industrial X-type zeolite) and its specific surface area in the present invention. FIG. 8 is a graph showing the ammonia adsorption amount of the water purification body in the present invention. FIG. 9 is a graph showing the ammonia adsorption amount of the water purification body in the present invention. FIG. 10 is a graph showing the amount of microorganisms attached to the water purifier in the present invention. FIG. 11 is a graph showing the air temperature and the water temperature at the time of evaluating the water purification function. FIG. 12 is a graph showing the results of water quality purification function evaluation (change in nitrogen concentration). FIG. 13 is a graph showing the results of water quality purification function evaluation (changes in phosphorus concentration). FIG. 14 is a graph showing the difference in water purification function between the example sample and the comparative example sample. FIG. 15 is a graph showing the weight distribution of reeds in the flow direction in the water purification function evaluation. FIG. 16 is a graph showing the results of biological regeneration evaluation.

  The water control structure of the present invention is a container or frame used for water control, wherein a water purification body comprising a binder and zeolite as essential raw materials, mixed and fired, and having a zeolite component in the composition of less than 50% by weight. It is characterized by being filled.

  The binder preferably contains a plastic clay raw material and / or a straw raw material.

  The plastic clay raw material mainly contains clay minerals such as kaolinite, halloysite, sericite and montmorillonite in its composition. Such plastic clay raw materials have been used for hundreds of years as clay raw materials for pottery in the Tokai region such as Aichi, Gifu and Mie, especially in the Tono region of Gifu prefecture. Porosity and low temperature sintering are excellent. Examples of the plastic clay material that can be used in the present invention include Kibushi clay, Sasame clay, Kaolin, Shale clay, Red clay, Ao clay, Ceramic stone, Bentonite, Waxite, Sepiolite, Attapulgite and the like. These can be used alone or in combination of two or more. In the present invention, kibushi clay, glazed clay, kaolin, shale clay, and porcelain are preferably used, and glazed clay and porcelain are more preferably used. Moreover, it is especially preferable to adjust the particle size of the plastic clay raw material to 5 μm or less because the strength of the water purification body can be improved.

  The raw material for the glaze is generally called a glaze and a glaze, and is a thin glassy silicic acid mixture applied to the surface of the ceramic. In the present invention, this soot raw material is one component that can constitute a water purification body, and has the effect of adjusting its plasticity, increasing its strength, and controlling the amount of pores. Examples of such raw materials for straw include, but are not limited to, for example, feldspar such as potassium feldspar, soda feldspar, pegmatite feldspar, aplite, algae (mackerel), magnesite, dolomite, limestone, talc, wollastonite, frit, etc. These may be used alone or in combination of two or more. In the present invention, feldspar, magnesite, dolomite, and limestone are preferably used from the viewpoint of cost reduction and strength development. In addition, magnesite is a magnesium carbonate mineral, also known as a rhododendron ore, and dolomite is a calcium and magnesium carbonate mineral, also called a dolomite.

  The raw material composition of the binder may be appropriately determined depending on the zeolite to be used, the cost of the water purification body, the desired strength, etc., and is not particularly limited. For example, when industrial synthetic zeolite is used as the above-mentioned zeolite, moldability is ensured. For this purpose, a binder containing a plastic clay raw material as an essential component is used, and the straw raw material can be appropriately blended for the purpose of improving the strength of the water purification body. In addition, when a component other than the zeolite component is included in the composition and a natural zeolite or a coal ash synthetic zeolite having originally relatively good plasticity is used as the above zeolite, only the soot raw material can be blended as a binder. .

  Moreover, when using the binder which mixed the plastic clay raw material and the straw raw material, it is preferable that the said plastic clay raw material is contained 30 to 95 weight% in a binder, and it is more preferable that 40 to 70 weight% is contained. Moreover, it is preferable that 5-70 weight% is contained in the binder, and, as for the said raw material, it is more preferable that 20-50 weight% is contained. Furthermore, since the optimal blending ratio of the plastic clay raw material and the straw raw material varies depending on the combination of the plastic clay raw material and the straw raw material that are actually used, it is desirable to obtain them appropriately. For example, in order to make the water purification body excellent in strength and porosity, when using a clay clay as a plastic clay raw material, and using any one of feldspar, dolomite, and limestone as a raw material, 40 ~ 60% by weight, feldspar, dolomite, or limestone is preferably 40-60% by weight, and when using clay as a plastic clay raw material and magnesite as a raw material, It is preferable that 70 to 90% by weight and magnesite be 10 to 30% by weight.

  It should be noted that those skilled in the art will be able to fully understand the plastic clay raw material and the koji raw material from the above description. For more details, please refer to “The Ceramic Society of Japan, Ceramics Engineering”. See pages 581 to 585 and pages 589 to 595 of Handbook (2nd edition) [Application], published by Gihodo Publishing Co., Ltd.

Examples of the zeolite used as the raw material for water purification in the present invention include natural zeolite such as clinoptilolite and mordenite, synthesis of A type, X type, Y type, USY type (ultra stable Y type), ZSM-5 and the like. Zeolite may be mentioned, but it is not particularly limited as long as it has a heat resistance of 500 ° C. or more and a cation exchange capacity of 100 meq / 100 g or more or a specific surface area of 300 m ² / g or more. From the viewpoint of cost and environmental protection, natural zeolite is preferable. In the present invention, a porous body having various characteristics of zeolite may be used as zeolite. The porous body having the characteristics of zeolite includes, for example, a mesoporous body (mesoporous material) having a pore diameter of 2 to 50 nm and a very narrow pore size distribution, and more specifically, Examples thereof include FSM-16 and MCM-41.

  Also, as the above zeolite, coal ash, molten slag, silicon sludge, water and sewage sludge incineration ash, waste incineration ash, paper sludge, casting sludge, tuff, volcanic ash, gravel waste, aluminum dross, aluminum-containing waste liquid, silicon-containing waste liquid, etc. It is also possible to use zeolite produced by alkali treatment of the waste. Examples of such zeolites include faujasite, philipsite, hydrated sodalite, and the like. Although not particularly limited, in the present invention, coal ash synthetic zeolite is preferably used, and coal ash synthetic X-type zeolite, It is more preferable to use either one of the coal ash synthesis Y-type zeolite and the coal ash synthesis A-type zeolite or two or more of them at the same time. Coal ash generated from coal-fired power plants is increasing year by year, and most of them are currently used effectively as admixtures for cement. Coal that will increase in the future when used as zeolite in the present invention. Ashes can be used effectively, and it is possible to contribute to cost and environmental protection. Coal ash contains 45-74% silica and 16-38% alumina in composition, but crystalline parts such as mullite and quartz cannot be easily dissolved in an alkaline aqueous solution. The zeolite conversion rate is about 15%, and research for increasing the synthesis rate is ongoing.

  It should be noted that the synthetic zeolite used in the present invention and the method for producing zeolite synthesized from waste and the raw material caivan ratio, alkali type, alkali concentration, pressure, stirring, temperature, etc. may be known production methods and conditions. There is no particular limitation.

  In addition to the binder and zeolite described above, coal ash may be directly added as a water purification body raw material in the present invention as long as the characteristics of the water purification body are not deteriorated. This also contributes to effective utilization of coal ash. be able to. The composition and physical properties of coal ash used in the present invention or the coal ash used in the above coal ash synthetic zeolite, such as the cayban ratio (silica / alumina ratio), are not particularly limited, but the calcium component is 15% by weight or less. Further, those having a lower content of sulfur, phosphorus and arsenic are preferred.

  Further, the water purification body raw material in the present invention may contain oxides of transition metals such as chromium, manganese, cobalt, nickel, antimony oxide, bengara (iron oxide), cupric oxide and the like for the purpose of coloring. Good. In addition to the above waste, glass powder, foundry sand, glitter, cerven (ceramic waste), stone powder (quarrying waste) Material), slag-based waste, and the like.

  The water purification body used in the present invention is manufactured by kneading a binder and zeolite, which are essential raw materials, and various additives added as necessary with an appropriate amount of water, forming the desired shape, and firing. Can do. The blending amount of each essential raw material may be blended so that the zeolite component after firing is less than 50% by weight, and is not particularly limited, but the binder may be 50 to 98% by weight and the zeolite may be less than 50% by weight. preferable. According to this, it is possible to obtain a water purification body that is lower in cost than conventional products, has a strength equal to or higher than that of concrete while maintaining porosity, and is remarkably superior in ammonia adsorption than activated carbon. It becomes. In addition, if the blending amount of the zeolite is a normal synthetic zeolite, the blending amount can be regarded as the zeolite component in the water purification body as it is, but in the case of natural zeolite or coal ash synthetic zeolite, the zeolite component Since many substances other than these are contained, the blending amount cannot be regarded as a zeolite component in the water purification body as it is. That is, even if the blending amount of natural zeolite or coal ash synthetic zeolite exceeds 50% by weight, if the zeolite component contained in the water purification body is less than 50% by weight, it can be treated as the water purification body used in the present invention. it can.

  In addition, the firing conditions at the time of firing may be appropriately determined depending on the shape, size, etc. of the water purification body, and are not particularly limited, but the water purification body in the present invention is obtained by carefully selecting the binder as the raw material. Since it is possible to sinter at a lower temperature than in the past, it is desirable to set the temperature as low as possible to maintain the porosity of the zeolite. Specifically, it is preferably calcined at a temperature of 500 to 700 ° C. for about 30 minutes to 2 hours. When A-type zeolite, X-type zeolite, Y-type zeolite and coal ash synthetic zeolite are used, 600 to 650 ° C., When using high silica type zeolite such as natural zeolite or USY type zeolite, it is more preferable to calcine at 600 to 700 ° C. for about 1 hour. If the calcination temperature is less than 500 ° C., sufficient strength cannot be given to the molded body. If it exceeds 700 ° C., the bending strength is improved, but the ion exchange capacity and adsorption force are reduced due to the change in the crystal structure of the zeolite. Especially, in the vicinity of 1000 ° C., the zeolite becomes amorphous, so that all of its excellent chemical properties are impaired.

  The forming method is not particularly limited. For example, the forming method can be performed by a ceramic manufacturing method for mass production such as casting molding, press molding, extrusion molding, or mechanical potting molding. Moreover, the shape and dimension can be processed as desired and are not particularly limited.

The water purification body in the present invention preferably has a specific surface area of 20 m ² / g or more and a bending strength of 2 MPa or more, a specific surface area of 30 m ² / g or more and a bending strength of 3 MPa or more. More preferably.

  Since the water purification body as described above has a composition ratio of the zeolite component of 50% by weight or less and the blending ratio of the binder is increased, it has higher strength and higher molding than the conventional zeolite-containing water purification body. A degree of freedom and low cost can be achieved. Furthermore, although the proportion of the zeolite component is less than 50% by weight compared with the conventional zeolite-containing water purification body, excellent porosity is realized, and the adsorption performance is equal to or higher than that of activated carbon. That is, the water purification body used in the present invention is excellent in productivity, strength, flexibility in molding, economy, and water purification function, and can be said to be suitable as a clog for water control.

  In addition, the water purification body used in the present invention not only has excellent ammonia nitrogen adsorption performance, but also has the ability to immobilize microorganisms comparable to activated carbon. Therefore, ammonia nitrogen adsorbed on the water purification body is more efficient by microorganisms. Nitrification and desorption. Therefore, the adsorption performance of the water purification body can be maintained over a long period of time, and it can greatly contribute to the improvement of the water purification function.

  Moreover, the shape of the water purification body used in the present invention is not particularly limited, but is preferably a hollow shape. By making it hollow, the contact area with water and the residence time of water increase, and it becomes possible to improve the water purification function. Moreover, it is more preferable that the surface of the purification body has an uneven shape. According to this, the contact area with water is further increased, and the adhesion of microorganisms is also improved. FIGS. 1A and 1B show an embodiment of a water purification body having a plurality of irregularities on a hollow surface. Since the water purification body in the present invention has a high degree of freedom in molding, it can be easily produced by a known extrusion molding method or press molding method.

  In addition, the size of the water purification body in the present invention is not particularly limited as long as it is a size that does not come out between the ridges and the frame to be used, but if it is too large, not only is it difficult to handle, but the specific surface area becomes small and the water quality This is not preferable because the purification function is lowered. Considering these balances, the minimum size of the water purification body is preferably in the range of φ40 to 150 mm.

  As the paddle filled with the water purification body as described above, it may be one generally used in water control works such as revetment work, for example, a rectangular parallelepiped futon paddle made of a wire net or a resin net, a cylinder The shape of a gabion can be mentioned. Similarly, the frame for filling the water purification body may be a frame generally used in water control works such as a sinking work, for example, a structure constructed by assembling wood or concrete into a tubular shape. . Of course, the collar and the frame in the present invention are not limited to these, and can be appropriately modified in material, shape and size depending on the installation location and other situations.

  Further, the water control structure of the present invention is formed by filling the water purification body in the present invention into the above-mentioned tub or frame, but the amount of water purification body to be filled is the water quality all over the tub or the frame. It may be filled with a purification body, and some of them may be mixed with activated carbon, cobblestone, pumice stone, pumice stone, customary soil, etc., which are usually used for water control, and are not particularly limited. FIG. 3 shows an embodiment of a water control structure 5 according to the present invention in which a water purification body 4 is filled in a futon bowl 3 generally used for revetment.

  Moreover, it is preferable that the plant is vegetated to the filled water purification body. By planting the plant, it is possible to further improve the efficiency of the water purification function, not only by revegetation of the revetment, but also by the symbiotic action of the plant and microorganisms and the action of the plant sucking up nitrogen and phosphorus components as nutrients. Become. However, in order to prevent the nitrogen and phosphorus components absorbed by the plant from returning to the water as much as possible, it is desirable to leave the root of the plant and harvest it at least once a year.

  The plant to be vegetated in the water purification body is not particularly limited, but is preferably an aquatic plant, more preferably at least one selected from the group consisting of reed, llama and makomo, and reed. Particularly preferred. Since this reed has the property of releasing oxygen from the roots, it is an optimal plant for the present invention in which it is an object to provide an environment suitable for aquatic organisms. In addition, as a method for vegetation planting, an optimal method may be appropriately determined according to the type of plant to be used, and is not particularly limited. For example, a plant seedling is inserted into a gap between the filled water purification bodies. It can be vegetated by sowing or seeding. FIG. 4 shows an embodiment in which a plant 7 is vegetated on the water purification body 4 inside the water control structure 5 of FIG. 3, and FIG. 5 shows a frame material 8 constructed by assembling concrete members. An embodiment of a state where a plant 7 is vegetated on the filled water purification body 4 is shown.

  The concrete block for water control according to the present invention is characterized in that the water purification body is fixed on the concrete block surface and / or contained in the porous concrete disposed on the surface of the concrete block. To do.

  The water purification block according to the present invention can be obtained by fixing and integrating the above water purification body on the surface of a known concrete block. In this case, the shape of the water purification body is matched to the plane of the concrete block. Thus, it is preferable to have a plate shape. Furthermore, when the water purification body has a flat plate shape, it is more preferable that the opposite surface in contact with the concrete block has an uneven shape. Moreover, it is preferable that the said concrete block is a porous concrete block with a larger porosity than normal concrete, and it is more preferable that the porosity is 20% or more. By using porous concrete, microorganisms are likely to adhere even at locations where the water purification body is not fixed, and the water purification function is improved. FIG. 2 shows an embodiment of a concrete block for water control according to the present invention in which a flat water quality purification body 2 is fixed and integrated on the upper surface of the concrete block 1. As a method for manufacturing a concrete block for water control as shown in FIG. 2, for example, a flat water purification body is fixed and integrated on the surface of an existing concrete block with an adhesive or a fixing bracket, Concrete can be poured into a mold having a predetermined shape, a flat water purification body can be installed thereon, and the purification body can be fixed and integrated simultaneously with the solidification of the concrete, and is not particularly limited.

  Moreover, the concrete block for water control according to the present invention can be obtained by arranging porous concrete containing the above water purification body having a size of several millimeters to about 10 millimeters on the surface of a normal concrete block. Furthermore, by using porous concrete made of a known low alkaline cement containing magnesium oxide as a component as the porous concrete, it is possible to further improve the adhesion of microorganisms and the water purification function.

  The water control method of the present invention is characterized in that the above-described water control structure and / or concrete block for water control is installed on the shore or bottom of a river or lake, and the installation form thereof is publicly known. There is no particular limitation as long as the water works such as revetment works and sinking works are performed. When preparing and installing the water control structure according to the present invention, the cage or frame previously filled with the water purification body may be transported to the installation site and sequentially installed at a predetermined location. Then, after assembling the eaves and the frame and installing them at a predetermined location, the water purification body may be filled. Although not particularly limited, the latter is preferable in consideration of work efficiency. The plant to be vegetated may be vegetated in advance in the water purification body, or after filling the water purification body on the installation site, the plant may be inserted into the gap to be vegetated. FIG. 6 shows an embodiment in which the water control structure 5 of FIG.

  According to the water control system of the present invention, a zeolite-containing water purification body having a specific composition filled or fixed to a water control structure or a concrete block for water control works, efficiently adsorbs ammonia nitrogen that causes water pollution. However, the regeneration mechanism by nitrification / desorption of the microorganisms carried on the purification body can maintain the water purification function for a long time, and can significantly improve the water quality of rivers and lakes without maintenance. Moreover, if a plant is vegetated on the water purification body, the water purification function is further enhanced by the symbiotic action of the plant and microorganisms and the absorption action of nitrogen and phosphorus of the plant, and the greening of the waterside space, biodiversity It is possible to create a space.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

(Characteristic evaluation of water purification body)
Example 1
95% by weight binder containing 35% by weight clay, 5% by weight porcelain stone, and 60% by weight algal silica, and industrial X-type zeolite (trade name 13Xpowder, manufactured by Union Showa Co., Ltd., specific surface area 430 m ² / g ) Mix 5% by weight and water equivalent to the binder to make mud, fill it with gypsum mold (cross section width 10mm, thickness 10mm, length 70mm), dehydrate after about 10 minutes dehydration And dried indoors for 1 day. Subsequently, this was baked by holding at a heating rate of 100 ° C./hr and 600 ° C. for 1 hour in an electric furnace to prepare a water purification body sample. Table 1 shows the composition of each component of Sasame clay, pottery stone, and algae used in the binder.

Example 2
A water purification body sample was prepared in the same manner as in Example 1 except that the binder was 90% by weight and the industrial X-type zeolite was 10% by weight.

Example 3
A water purification body sample was prepared in the same manner as in Example 1 except that the binder was 70% by weight and the industrial X-type zeolite was 30% by weight.

Example 4
A water purification sample was prepared in the same manner as in Example 1 except that the binder was 70% by weight, the industrial X-type zeolite was 5% by weight, and further coal ash (manufactured by Techno Chubu Co., Ltd.) was 25% by weight. . The composition (%) of the coal ash is shown in Table 2.

Example 5
A water purification body sample was prepared in the same manner as in Example 1 except that 70% by weight of binder, 10% by weight of industrial X-type zeolite, and 20% by weight of coal ash were further blended.

Example 6
A water purification body sample was prepared in the same manner as in Example 1 except that 70% by weight of the binder, 20% by weight of the industrial X-type zeolite, and 10% by weight of coal ash were further blended.

Example 7
Except for using 60% by weight of binder and 40% by weight of clinoptilolite (product name: Iwamilite 200 mesh, specific surface area 45.6 m ² / g, zeolite component 45.3%) as zeolite. A water purification body sample was prepared in the same manner as in Example 1.

Comparative Example 1
A water purification body sample was prepared in the same manner as in Example 1 except that the binder was 70% by weight, and 30% by weight of coal ash was blended without blending industrial X-type zeolite.

  About each sample of the said Examples 1-7 and the comparative example 1, the porosity, the bulk specific gravity, the pore volume, the specific surface area, and the bending strength were measured by the method shown below. The results are shown in Table 3.

Porosity: The sample was dried at 110 ° C., and the weight when it became a constant weight was defined as W1. Next, the sample is put in water, boiled for 3 hours or more, air in the pores is completely released, cooled in water, and the weight when the sample is suspended in water is W2. Further, the sample is taken out of the water, only the surface is quickly wiped with a compress, water drops are taken, the weight is quickly measured, and this is designated as W3. The porosity is calculated using W1, W2, and W3 and the following equation.
Porosity = {(W3-W1) / (W3-W2)} × 100

Pore volume: Measured in a pressure range of 1 to 60000 psi using a mercury porosimeter (manufactured by Yuer Sonics, poremaster 60) (mercury intrusion method).

Specific surface area: 5 using a specific surface area measuring device (manufactured by Yourcionix, Auto Soap 1) and a measurement range of 0.05 to 0.35 in terms of equilibrium relative pressure (P / P ₀ ) by the gas dissolution BET method. The point was measured (JIS Z 8830).

Bending strength: Using UCT-5T manufactured by Orientec, place a sample on two fulcrums arranged at a span of 30 mm, and apply a load with a crosshead speed of 0.5 mm / min to one central point between the fulcrums. The maximum load until the sample was broken was measured. The bending strength Tr was obtained by the following formula.
Tr = 3WL / 2bd ² (W: Maximum load (N), L: Distance between lower fulcrums (mm), b: Width of test specimen (mm), d: Thickness of test specimen (mm)) )

  As shown in Table 3, the water purification body samples of Examples 1 to 7 have a ratio of 3 to 10 times that of the water purification body sample of Comparative Example 1 even though the zeolite content is lower than the binder content. Has a surface area. Moreover, the bending strength of the water purification body sample of Examples 1-7 showed the strength characteristic more than concrete and 3-7 Mpa. Further, other characteristics showed values equal to or higher than those of the comparative example. The porous characteristics of the samples of these examples are comparable to existing advanced catalytic water purification bodies (for example, Japanese Patent Application Laid-Open No. 11-246282, Japanese Patent Application Laid-Open No. 11-314913, etc.). It is. Therefore, it turns out that the sample of Examples 1-7 is a favorable water quality purification body manufactured without impairing the pore structure which zeolite has.

  Next, using a coal ash synthetic X-type zeolite, a water purification body was prepared and its characteristics were evaluated.

Example 8
Mix mud with 35% by weight of clay, 5% by weight of porcelain stone, 85% by weight of binder containing 60% by weight of algae, 15% by weight of coal ash synthetic X-type zeolite, and water equivalent to the binder. It was prepared, filled in a plaster mold (cross-sectional width 10 mm, thickness 10 mm, length 70 mm), dehydrated for about 10 minutes, demolded, and dried indoors for 1 day. Subsequently, this was baked by holding at a heating rate of 100 ° C./hr and 600 ° C. for 1 hour in an electric furnace to prepare a water purification body sample. In addition, the said coal ash synthetic | combination X-type zeolite is produced | generated using the continuous manufacturing apparatus disclosed by Unexamined-Japanese-Patent No. 2002-187715 from the coal ash (made by Techno Chubu Co., Ltd.) of Table 2.

Example 9
A water purification body sample was prepared in the same manner as in Example 8 except that the coal ash synthetic X-type zeolite was changed to 30% by weight.

Example 10
A water purification body sample was prepared in the same manner as in Example 8 except that the coal ash synthetic X-type zeolite was 30% by weight and the temperature at the time of calcination was 700 ° C.

Example 11
A water purification body sample was prepared in the same manner as in Example 8 except that the coal ash synthetic X-type zeolite was 30% by weight and the temperature at the time of calcination was 800 ° C.

Comparative Example 2
A water purifier sample was prepared in the same manner as in Example 8 except that the binder component of Example 8 was 100% by weight and the temperature during firing was 700 ° C. without blending the zeolite component.

Comparative Example 3
A water purification sample was prepared in the same manner as in Example 8, except that the binder component of Example 8 was 100% by weight and the calcination temperature was 800 ° C. without blending the zeolite component.

  For each sample of Examples 8 to 11 and Comparative Examples 2 and 3, the porosity, water absorption, bulk specific gravity, specific surface area, pore volume and bending strength were measured. The results are shown in Table 4. In addition, the measuring method of a water absorption rate is as follows, and the other measurement is the same as the above-mentioned method.

Water absorption rate: Calculated by using W1, W2, and W3 measured in the above-described method for measuring porosity and the following equation.
Water absorption rate = {(W3-W1) / W1} × 100

  As shown in Table 4, the water purification bodies of Examples 8 to 10 have a specific surface area approximately four times that of Comparative Examples 2 and 3 which are general porous ceramics, and exhibit excellent porous properties. . Also, the bending strength is 1.5 MPa or more, indicating strength characteristics corresponding to concrete. Further, as shown in Example 11, when the firing temperature was 800 ° C., the bending strength of the water purification body was improved, but the specific surface area was greatly reduced, and there was no difference from Comparative Examples 2 and 3. This is presumably because the specific surface area was greatly reduced by making the zeolite amorphous.

  Next, the water purification body which contains a natural zeolite as a main component was prepared, and the characteristic evaluation was implemented.

Example 12
Dolomite (manufactured by Ueda Coal Manufacturing Co., Ltd.) 20% by weight as a binder, and clinoptilolite (manufactured by Mitsui Kinzoku Resources Co., Ltd., trade name Iwamilite 200 mesh, specific surface area 45.6 m ² / g, zeolite component 45.3%) as a natural zeolite ) Mix 80% by weight of water with an equivalent amount of binder and make mud, fill it with gypsum mold (cross-sectional width 10mm, thickness 10mm, length 70mm), dehydrate after about 10 minutes dehydration And dried indoors for 1 day. Subsequently, this was baked by holding at a heating rate of 100 ° C./hr and 600 ° C. for 1 hour in an electric furnace to prepare a water purification body sample.

Example 13
A water purification body sample was prepared in the same manner as in Example 12 except that instead of dolomite, 20% by weight of a binder containing 75% by weight of Sasame clay and 25% by weight of magnesite (manufactured by Kamishima Chemical Industry) was used.

Example 14
A water purification body sample was prepared in the same manner as in Example 12 except that Niijima feldspar (manufactured by Marumi Porcelain) was used as a binder instead of dolomite.

Comparative Example 4
100% by weight of clinoptilolite was used as a water purification body sample.

  For each sample of Examples 12 to 14 and Comparative Example 4, the porosity, bulk specific gravity, specific surface area, and bending strength were measured. The results are shown in Table 6. Note that the measurement method is the same as that described above. Table 5 shows the compositions of the dolomite, magnesite, and Niijima feldspar.

  Next, the relationship between the blending amount of zeolite and the specific surface area was examined.

Example 15
97% by weight of binder containing 35% by weight of Sasame clay, 5% by weight of porcelain stone, and 60% by weight of algae, and industrial X-type zeolite (made by Union Showa Co., Ltd., trade name: 13X powder, specific surface area of 430 m ² / g ) 3% by weight was mixed with a mixer (MHS-100, manufactured by Miyazaki Tekko Co., Ltd.) for 2 minutes, and then 20% by weight of water was added to the mixed raw material, and mixed again with a mixer for 2 minutes. Next, the mixture was filled in a plaster mold (cross-sectional width 10 mm, thickness 10 mm, length 70 mm), dehydrated for about 10 minutes, demolded, and dried indoors for 1 day. Subsequently, this was baked by holding at a heating rate of 100 ° C./hr and 600 ° C. for 1 hour in an electric furnace to prepare a water purification body sample. The specific surface area of this sample was measured by the same method as described above. The results are shown in Table 7.

Example 16
Mixer (Miyazaki Tekko Co., Ltd.) with 95% binder by weight 35% by weight of clay, 5% by weight of porcelain stone, and 60% by weight of algae and 5% by weight of industrial X-type zeolite (made by Union Showa Co., Ltd.) After mixing for 2 minutes with MHS-100, manufactured by company, water was added in an external ratio of 22% by weight to the mixed raw material and mixed again for 2 minutes with a mixer. Next, the mixture was filled in a plaster mold (cross-sectional width 10 mm, thickness 10 mm, length 70 mm), dehydrated for about 10 minutes, demolded, and dried indoors for 1 day. Subsequently, this was baked by holding at a heating rate of 100 ° C./hr and 600 ° C. for 1 hour in an electric furnace to prepare a water purification body sample. The specific surface area of this sample was measured by the same method as described above. The results are shown in Table 7.

Example 17
Mixer (Miyazaki Tekko Co., Ltd.) with 90% binder by weight 35% by weight clay, 5% by weight porcelain stone, and 60% by weight algal silica and 10% by weight industrial X-type zeolite (made by Union Showa Co., Ltd.) After mixing for 2 minutes with MHS-100 manufactured by company, water was added in an external ratio of 25% by weight to the mixed raw material and mixed again for 2 minutes with a mixer. Next, the mixture was filled in a plaster mold (cross-sectional width 10 mm, thickness 10 mm, length 70 mm), dehydrated for about 10 minutes, demolded, and dried indoors for 1 day. Subsequently, this was baked by holding at a heating rate of 100 ° C./hr and 600 ° C. for 1 hour in an electric furnace to prepare a water purification body sample. The specific surface area of this sample was measured by the same method as described above. The results are shown in Table 7.

Example 18
Mixer of 50.5% by weight of binder containing 35% by weight of clay, 5% by weight of porcelain stone, and 60% by weight of algae and 49.5% by weight of industrial X-type zeolite (made by Union Showa Co., Ltd.) After mixing for 2 minutes (MHS-100, manufactured by Miyazaki Tekko Co., Ltd.), 48% by weight of water was added as an external ratio to the mixed raw material, and mixed again for 2 minutes with a mixer. Next, the mixture was filled in a plaster mold (cross-sectional width 10 mm, thickness 10 mm, length 70 mm), dehydrated for about 10 minutes, demolded, and dried indoors for 1 day. Subsequently, this was baked by holding at a heating rate of 100 ° C./hr and 600 ° C. for 1 hour in an electric furnace to prepare a water purification body sample. The specific surface area of this sample was measured by the same method as described above. The results are shown in Table 7.

  FIG. 7 shows the relationship between the amount of X-type zeolite added and the specific surface area obtained from the results of Examples 1-6 and Examples 15-18. From FIG. 7, the relationship between the X-type zeolite addition amount and the specific surface area shows a linear correlation, and the specific surface area increase is almost the same as the increase value due to the X-type zeolite addition amount. This result shows that the samples of Examples 1 to 6 and Examples 15 to 18 are good water purification bodies produced without impairing the pore structure of zeolite.

(Adsorption characteristics)
Next, in order to evaluate the adsorption performance of the water purification body used in the present invention, ammonia adsorption was performed using the samples prepared in Examples 8 and 9 and Comparative Example 3, and commercially available activated carbon (specific surface area 847 m ² / g). A test was conducted.

In the test method, 500 ml of NH ₄ Cl solution was prepared in a 500 ml Erlenmeyer flask with an ammonia concentration in the range of 20 to 400 mg / L, and each sample (particle size 1.5 to 2.0 cm) and activated carbon 40 to 60 cm ^{3 were} added. After shaking with a constant temperature shaker at 30 ° C. and 70 rpm until the adsorption equilibrium was reached, the ammonia adsorption amount of each sample and activated carbon was measured. The results are shown in FIG. In addition, the apparatus and measurement conditions used for the measurement of adsorption amount are as follows.

Measurement equipment Tosoh ion chromatograph TOSOH CO-8011 (detector TOSOH UV-8011, pump TOSOH CCPD)
Measurement conditions Absorption wavelength: 230 nm
Column: TSKgelIC-Anion-PW
Column thermostat: 40 ° C
Eluent: Anion standard solution Eluent flow rate: 1.2 ml / min

  As shown in FIG. 8, the water purification bodies of Examples 8 and 9 exhibited good ammonia adsorption characteristics and exhibited adsorption performance superior to that of activated carbon even though the zeolite component was about 2 to 5%.

Next, a sample (Example 19) in which the zeolite in the sample of Example 2 and the zeolite in the sample of Example 2 were A-type zeolite (trade name A4 powder manufactured by Union Showa Co., Ltd.), the sample of Example 7, and Example 7 An ammonia adsorption test was performed on four samples, which were mordenite (Mitsui Metal Resources Development, MG Iwamilite, specific surface area: 16.0 m ² / g), which was a sample (Example 20). .

Specifically, 450 ml of NH ₄ Cl solution was prepared in a 500 ml Erlenmeyer flask with an ammonia concentration in the range of 20 to 2000 mg / L, 50 g of each sample (particle size 1.5 to 2.0 cm) was added, and the mixture was shaken at a constant temperature. After shaking until the adsorption equilibrium was reached at 20 ° C. and 100 rpm, the ammonia adsorption amount of each sample was measured. The results are shown in FIG. The equipment and measurement conditions used for measuring the adsorption amount are the same as described above.

  As shown in FIG. 9, the water purification body of each Example showed good ammonia adsorption characteristics.

(Microbe adhesion)
Next, in order to evaluate the microbial adhesion of the water purification body, a batch-type microbial adhesion test was performed using the samples prepared in Examples 15 and 16 and activated carbon (specific surface area 847 m ³ / g).

In the test method, after suspending microorganisms (sludge) in 0.05 M PBS (phosphate buffer solution), both samples and activated carbon were added at 7.5 cm ³ per 100 ml of the suspension, and shaken at 135 rpm for about 5 hours. After the completion, the total organic carbon (TOC) of the supernatant was measured and subtracted from the TOC before the start of shaking to evaluate the amount of TOC (microorganism) attached to both samples and 7.5 cm ^{3 of} activated carbon. The results are shown in FIG.

  As shown in FIG. 10, the water purification bodies of Examples 15 and 16 showed the same level of microorganism adhesion as that of activated carbon.

(Evaluation of water purification function)
Next, the water purification function in a system in which plants were planted on the water purification body sample used in the present invention was evaluated as follows.

  First, a water purification body having the same composition as that of Example 2 molded into the shape (inner diameter 1.3 cm, maximum outer diameter 4.2 cm, length 6 cm) shown in FIG. A water quality purification body is filled over a length of 25.2m from a point of 2.4m from the inflow part to the end of the waterway of an artificial waterway (width 0.5m, depth 0.6m, length 27.6m). A system in which reeds are vegetated in the gap (Example 21), and instead of the water purification body of Example 2 above, river gravel (φ50-60 mm, sampled at Tone River) of the same size as this is the same as above A system (Comparative Example 5) in which artificial water channels were filled and reed was vegetated was prepared. Table 8 summarizes various conditions in each artificial channel.

Then, artificial polluted water and tap water (hereinafter referred to as inflow substrates) having the components shown in Table 9 are continuously allowed to flow into each of the artificial water channels at an inflow rate of 5 mL / min and 10 L / min for about 50 days, respectively. It was. The inflow start time is September 5, 2003, which is one month after August 4, 2003 when the filling of the water purification body and the planting of the reed are completed. Thereafter, sampling was performed at the inlet and outlet of the water purifier filling section every few days from the start of inflow, and the TN, NH ₄ -N, NOx-N, TP, and PO ₄ -P concentrations were measured. In addition, measurements other than TN and TP concentrations were measured after filtration with a 0.45 μm filter. Under these conditions, the residence time of the inflowing substrate in the system of Example 21 was 6 hours, and the residence time of the inflowing substrate in the system of Comparative Example 5 was 3 hours. In FIG. 11, the data of the air temperature at the time of sampling and the water temperature in the inflow part of the system of Example 21 are shown.

  12 and 13 show changes with time in each system of nitrogen and phosphorus concentrations. Immediately after the start of measurement, no NOx was produced in the system of Example 21, but NOx was produced in the system of Comparative Example 5. This is probably because nitrifying bacteria existed in the soil originally attached to the gravel, and the reed rhizosphere became a microorganism house, so that the system was stabilized earlier than the system of Example 21. In addition, regarding the system of Example 21, the inflow NOx concentration exceeded the inflow NOx concentration 29 days after the start of the experiment, and it was observed that the action of nitrifying bacteria became active from this time. It was suggested to function as a niece. On the other hand, looking at the time course of phosphorus in each system, it can be seen that any system has been removed throughout the evaluation period. In general, the phosphorus removal rate in the contact oxidation method is low, and there are many examples of about several percent, but the method combining vegetation purification and contact oxidation often shows a high removal rate of 70-80%. Seems to have incorporated phosphorus as nutrients.

The average removal rates of TN, NH ₄ -N and TP of each system during the evaluation period are shown in FIG. It can be seen that the average removal rates of TN, NH ₄ -N and TP of the system of Example 21 are all higher than that of the system of Comparative Example 5. Specifically, in particular, the TN and NH ₄ -N average removal rates were more than twice, and the TP average removal rate was 1.3 times wider. Therefore, it was proved that the water purification body filled in the system of Example 21 had an excellent water purification function as compared with the conventional one.

(Yoshi's growth data)
After the evaluation of the water purification function is completed, the inflow substrate continues to flow in, and on December 10, 2003, the reeds that are vegetated on the water purification bodies or gravel of each system are cut, and the total number, weight, The nitrogen content and phosphorus content were measured, and the growth of reed was compared. Table 10 shows the results. Moreover, the weight distribution of the flow direction at the time of reap cutting is shown in FIG.

  Although it was confirmed that the growth of the reed of Example 21 was remarkable even during the evaluation period, it was confirmed from Table 8 that the reed of the system of Example 21 grew more than the reed of the system of Comparative Example 5. It was clear that the water purification body sample packed in the system of Example 21 had an excellent water purification function. In addition, from FIG. 15, the average weight of the reed grown in the system of Comparative Example 5 is increased at each point, whereas the reed grown in the system of Example 21 is upstream of the water channel rather than the downstream of the water channel. It can be seen that the weight is greatly increased in the middle stream region. This is thought to be the result of the ammonia adsorption amount prevailing in the upstream to middle basin because the substrate was introduced from the upstream, and nitrification by microorganisms and absorption into the plant being actively performed. Note that the water purification function evaluation period is only two months, and if the long-term evaluation is continued, the difference between upstream and downstream will be resolved with the passage of time, and the water purification function as a whole system will be enhanced.

(Biological regeneration evaluation)
Here, the ammonia desorption promoting effect of the water purification body samples of Example 2 and Example 7, that is, the biological regeneration was evaluated.

200 g of each of the samples of Example 2 and Example 7 was put into 1 L of an aqueous solution having a concentration of 10 mg-NH 4 ⁺ / L and stirred for 48 hours, then washed with pure water and dried at 60 ° C. for 42 hours. Each sample was saturated with ammonia. Next, 40 g of each ammonia saturated sample was immersed in 480 mL of a mixture of diluted water and sludge (MLSS 1000 mg / L) and shaken at 20 ° C. and 120 rpm (shaker: manufactured by Tokyo Rika Kikai Co., Ltd.). MMS-300), and each NH ₄ -N, NO ₂ -N, NO ₃ -N concentration was measured over time. The results are shown in FIG. The diluted water used is the inflow of the artificial water channel in the Ecological Park in Saitama Prefectural Environmental Science Center using a 0.2 μm filter, and the sludge is aerated at the farmer's drainage treatment plant in Kamisai, Saitama Prefecture. The tank was centrifuged and washed with pure water.

As shown in FIG. 16, the sample of Example 2 and 7, under the NH ₄ ⁺ supply from work saturated zeolite shaped body of the microorganism, NO ₃ ^- generation was observed in, NH ₄ ⁺ desorption reaction with nitrification It can be seen that promotion and removal thereof, that is, biological regeneration is performed. Therefore, it can be seen that the water purification body of the present invention does not require maintenance such as replacement and processing of the carrier semipermanently.

  It will be appreciated by those skilled in the art that the foregoing is a preferred embodiment of the invention and that many changes and modifications can be made without departing from the spirit and scope of the invention.

Claims (23)

It is characterized by mixing and firing a binder and zeolite as essential raw materials, and filling a water purifier having a zeolite component of less than 50% by weight in a pot or frame used for water control. Water control structure. 2. The water control structure according to claim 1, wherein the binder contains a plastic clay raw material and / or a straw raw material. The water control structure according to claim 2, wherein the plastic clay raw material is one or more selected from the group consisting of Kibushi clay, Sasame clay, kaolin, shale clay, and porcelain stone. . The water control structure according to claim 2 or 3, wherein a particle diameter of the plastic clay raw material is 5 µm or less. 3. The water control structure according to claim 2, wherein the straw raw material is one or more selected from the group consisting of feldspar, magnesite, dolomite, and limestone. One selected from the group consisting of natural zeolite, synthetic A-type zeolite, synthetic X-type zeolite, synthetic Y-type zeolite, coal ash synthetic A-type zeolite, coal ash synthetic X-type zeolite, and coal ash synthetic Y-type zeolite Or it is 2 or more types, The water control structure in any one of Claims 1-5 characterized by the above-mentioned. The temperature at the time of baking of the said water purification body is 500-700 degreeC, The water control structure in any one of Claims 1-6 characterized by the above-mentioned. The water control structure according to any one of claims 1 to 7, wherein the water purification body has a specific surface area of 20 m ² / g or more and a bending strength of 2 MPa or more. The water control structure according to any one of claims 1 to 8, wherein the water purification body has a hollow shape. The water control structure according to any one of claims 1 to 9, wherein a plant is vegetated on the water purification body. The water control structure according to claim 10, wherein the plant is at least one selected from the group consisting of reed, cattail, and macomo. A water purification body comprising a binder and zeolite as essential materials mixed and fired, and having a zeolite component in the composition of less than 50% by weight is fixed on the concrete block surface, and / or the concrete block surface portion A concrete block for waterworks, which is contained in porous concrete arranged in The concrete block for water control construction according to claim 12, wherein the binder contains a plastic clay raw material and / or a straw raw material. The said plastic clay raw material is 1 type, or 2 or more types selected from the group which consists of Kibushi clay, Sasame clay, Kaolin, shale clay, and porcelain stone Concrete block. The concrete block for water control according to claim 13 or 14, wherein the plastic clay raw material has a particle size of 5 µm or less. 14. The concrete block for water control according to claim 13, wherein the raw material for dredging is one or more selected from the group consisting of feldspar, magnesite, dolomite, and limestone. One selected from the group consisting of natural zeolite, synthetic A-type zeolite, synthetic X-type zeolite, synthetic Y-type zeolite, coal ash synthetic A-type zeolite, coal ash synthetic X-type zeolite, and coal ash synthetic Y-type zeolite Or it is 2 or more types, The concrete block for water control works in any one of Claims 12-16 characterized by the above-mentioned. The concrete block for water control works according to any one of claims 12 to 17, wherein a temperature during firing of the water purification body is 500 to 700 ° C. Wherein a specific surface area of the water purifier is 20 m 2 / ^g or more and a bending dikes Engineering for Concrete block according to any one of claims 12 to 18 in which the intensity is equal to or not less than 2 MPa. The water purification concrete block according to any one of claims 12 to 19, wherein the water purification body has a hollow shape. The concrete block for water control according to any one of claims 12 to 20, wherein a plant is vegetated on the water purification body. The concrete block for water control works according to claim 21, wherein the plant is at least one selected from the group consisting of reed, catfish and makomo. A water control structure according to any one of claims 1 to 11 and / or a concrete block for water control according to any one of claims 12 to 22 is installed on the shore or bottom of a river or lake. Water construction method to do.

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